Abstract
Thin films of stable metal-organic frameworks (MOFs) such as UiO-66 have enormous application potential, for instance in microelectronics. However, all-gas-phase deposition techniques are currently not available for such MOFs. We here report on thin-film deposition of the thermally and chemically stable UiO-66 in an all-gas-phase process by the aid of atomic layer deposition (ALD). Sequential reactions of ZrCl4 and 1,4-benzenedicarboxylic acid produce amorphous organic–inorganic hybrid films that are subsequently crystallized to the UiO-66 structure by treatment in acetic acid vapour. We also introduce a new approach to control the stoichiometry between metal clusters and organic linkers by modulation of the ALD growth with additional acetic acid pulses. An all-gas-phase synthesis technique for UiO-66 could enable implementations in microelectronics that are not compatible with solvothermal synthesis. Since this technique is ALD-based, it could also give enhanced thickness control and the possibility to coat irregular substrates with high aspect ratios.
Highlights
Thin films of stable metal-organic frameworks (MOFs) such as UiO-66 have enormous application potential, for instance in microelectronics
Organic–inorganic hybrid materials have been deposited as thin films by atomic layer deposition (ALD) in a mode known as molecular layer deposition (MLD)[10,11,12]
The growth rate is B6–7 Å cycle À 1 with a reaction temperature of 265 °C, which is notably higher than normal ALD-processes, but within what is expected for an ALD/MLD process
Summary
Thin films of stable metal-organic frameworks (MOFs) such as UiO-66 have enormous application potential, for instance in microelectronics. Thanks to the wide choice of inorganic and organic building units, the range of possible compounds is huge and only a fraction of these have been explored, especially with respect to characterization of their physical properties Due to their very high porosity, MOFs are promising for a number of applications such as gas storage[2], catalysis[3], drug delivery[4], handling and destruction of toxins[5,6,7], and as membranes for desalination[8]. Organic–inorganic hybrid materials have been deposited as thin films by atomic layer deposition (ALD) in a mode known as molecular layer deposition (MLD)[10,11,12] These films are typically amorphous and do not show the same properties as crystalline MOFs. ALD and MLD are techniques where two or more precursors are individually pulsed into a reaction chamber through the gas phase and allowed to react with, and saturate, the surface of a substrate. An all-gas-phase synthesis utilizing ALD/MLD of MOFs is a highly suitable approach with very precise control of the amount of deposited material
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